[0001] This invention relates to lubricant compositions for transmission of power, and more
particularly to lubricant compositions having excellent traction coefficient and wear
resistance, load carrying capacity, thermal stability, oxidation stability, rust preventing
property and being effectively utilized as the lubricants for power transmission having
a traction drive mechanism.
[0002] In recent years, traction drive (friction driving device utilizing rolling contact)
is employed as continuously variable transmission for automobile and industrial equipment,
etc. As the fluid used for the traction drive, a fluid having high traction coefficient
and high power transmitting efficiency is required.
[0003] Under the circumstances, a variety of proposals are made in order to obtain fluid
for traction drive having high power transmitting efficiency (for example, Japanese
Patent Publications Nos. 46-338, 46-339, 47-35763, 53-36105, 58-27838, Japanese Patent
Laid-open Publications No. 55-40726, 55-43108, 55-60596, 55-78089, 55-78095, 57-155295,
57-155296, 57-162795 and the like).
EP-A-0 220 426 relates to a lubricant composition for transmission of power essentially
consisting of (A) a base oil, (B) zinc dithiophosphate and/or oxymolybdenum organo-phosphorodithioate
sulfide and (C) at least one compound selected from phosphoric ester, phosphorous
ester, and their amine salts having improved wear resistance and fatigue life. For
example in EP-A-0 208 541 a lubricant compositions for use in traction drives are
described which incorporate a selected hydrocarbon type of base oils combined with
specified amounts of selected zinc dialkyldithio phosphates, alkenyl succinimides
or their boron derivatives, carboxylic acid esters of polyalcohols. However, such
composition is insufficient in oxidation stability. In EP-A-0 113 045 a lubricating
oil composition is described containing a base oil, a sulfurized oxymetal organo-phosphorodithioate,
zinc dithiophosphate, a calcium alkylbenzenesulfonate and/or a calcium petroleumsulfonate
which is used to reduce the mechanical friction loss of four-cycle engines. Also in
DE-A-18 06 401 and DE-A-31 27 970 lubricant compositions are described, however such
compositions do not fulfill the requirements of conventional problems such as wear
resistance and load carrying capacity and have poor thermal and oxidation stability.
[0004] It is necessary to lubricate the traction drive mechanism with a single oil since
said traction drive mechanism is consisted as an apparatus for transmission of power
containing gear machine, oil pressure mechanism, rolling bearings, etc. in the same
system.
[0005] However, the conventional fluids for the traction drive mentioned above had improved
the power transmitting efficiency, but since they were proposed exclusively for the
traction drive, when used at locations such as gear mechanism, oil pressure mechanism,
rolling contact bearing and the like, there are such problems as the wear resistance
and load carrying capacity were not sufficient, and moreover, the thermal and oxidation
stability were poor, and a large amount of sludges was generated, and they could not
sufficiently withstand for practical purposes.
[0006] Under the circumstances, in order to overcome the foregoing conventional problems,
blending of the additives such as extreme pressure additive, antiwear agent, antioxidant
to the fluid for traction drive described in the foregoing is considered.
[0007] But, when an additive such as extreme pressure additive is merely added to the fluid
for traction drive, problems such as shortening the fatigue life of the traction drive
mechanism or remarkably deteriorating the power transmitting efficiency or causing
corrosion, and as a result, the lubricant capable of satisfying sufficiently all the
characteristics which are appropriate for practical purpose has not been available.
[0008] An object of this invention is to provide lubricant compositions for transmission
of power having excellent traction coefficient and high power transmitting efficiency
and moreover excellent wear resistance, load carrying capacity, thermal and oxidation
stability, and rust preventing property and being effectively utilized for the lubrication
of the power transmission having the traction drive mechanism.
[0009] This invention is to provide, in the first place, a lubricant composition for transmission
of power which consists essentially of (A) a base oil whose main component is a saturated
hydrocarbon having condensed ring and/or non-condensed ring, (B) 0.1 to 2.0 weight
% to the whole composition of zinc dithiophosphate, provided that zinc dithiophosphate
of which R¹ - R⁴ denote a primary alkyl group of 3 - 30 carbon atoms is more than
30 weight % based on the whole zinc dithiophosphate, represented by the following
general formula (I)

in which R¹, R², R³ and R⁴ denote a primary alkyl group of 3 - 30 carbon atoms, secondary
alkyl group of 3 - 30 carbon atoms or aryl group of 6 - 30 carbon atoms, or alkyl
group substituted aryl group of 6 - 30 carbon atoms, provided that R¹, R², R³ and
R⁴ may be the same or different, and/or oxymolybdenum organophosphorodithioate sulfide
represented by the following general formula (II)

in which R⁵ and R⁶ denote an alkyl group of 1 - 30 carbon atoms, cycloalkyl group
of up to 30 carbon atoms, aryl group of up to 30 carbon atoms or alkylaryl group of
up to 30 carbon atoms, and x and y denote a positive real number satisfying x + y
= 4, provided that R⁵ and R⁶ may be the same or different, (C) 0.1 to 3.0 weight %
to the whole composition of alkenyl succinimide or its derivative and (D) 0.01 to
1.0 weight % to the whole composition of a rust inhibitor, which is calcium sulfonate
or barium sulfonate.
[0010] In this invention, as (A) component, the base oil whose main component is a saturated
hydrocarbon having condensed ring and/or non-condensed ring is used. As the saturated
hydrocarbon mentioned above, a variety of compounds can be enumerated, but particularly,
the saturated hydrocarbon having the cyclohexyl group and/or decalyl group, and the
saturated hydrocarbon of 10 - 40 carbon atoms is preferable. As the saturated hydrocarbon
having the cyclohexyl group and/or decalyl group, concretely speaking, the following
compounds can be enumerated.
[0011] Namely, for example,
2-methyl-2,4-dicyclohexyl butane represented by the following formula

1-decalyl-1-cyclohexyl ethane represented by the following formula

2-methyl-2,4-dicyclohexyl pentane represented by the following formula

alkyl cyclohexane represented by the following formula

in which R⁷ denotes alkyl group of 10 - 30 carbon atoms, can be enumerated. As the
example compounds, concretely speaking, isododecylcyclohexane and isopentadecylcyclohexane
can be enumerated.
[0012] Besides, as the saturated hydrocarbon having condensed ring and/or non-condensed
ring which is the (A) component in this invention, the following compounds can be
enumerated.
[0013] Namely,
1,2-di(dimethylcyclohexyl)propane represented by the following formula

2,3-di(methylcyclohexyl)-2-methylbutane represented by the following formula

1,2-di(mehtylcyclohexyl)-2-methylpropane represented by the following formula

2,4-dicyclohexyl pentane represented by the following formula

cyclohexyl methyl decalin represented by the following formula

1-(methyldecalyl)-1-cyclohexyl ethane represented by the following formulas

1-(dimethyldecalyl)-1-cyclohexyl ethane represented by the following formulas

2-decalyl-2-cyclohexyl propane represented by the following formula

cyclohexylmethyl perhydrofluorene represented by the following formula

1-perhydrofluorenyl-1-cyclohexyl ethane represented by the following formula

cyclohexylmethyl perhydroacenaphthene represented by the following formula

1,1.2-tricyclohexyl ethane represented by the following formula

bisdecalin represented by the following formula

2,4,6-tricyclohexyl-2-methylhexane represented by the following formula

2-(2-decalyl)-2,4,6-trimethylnonane represented by the following formula

1,1-didecalyl ethane represented by the following formula

tercyclohexyl represented by the following formula

1,1,3-trimethyl-3-cyclohexyl hydrindane represented by the following formula

and 2-methyl-1,2-didecalyl propane represented by the following formula

can be enumerated, and they may be used singly or in combination of more than two
kinds.
[0014] The (A) component in this invention is the base oil whose main component is the foregoing
saturated hydrocarbon having condensed ring and/or non-condensed ring, and in addition,
it may contain at a rate of less than 50 %, mineral oil, particularly, naphthene mineral
oil, synthetic oils such as polybutene, alkylbenzene.
[0015] Next, in this invention, as the (B) component, 0.1 to 2.0 weight % to the whole composition
of zinc dithiophosphate represented by the general formula (I) and/or oxymolybdenum
organophosphorodithioate sulfide represented by the general formula (II) is used.
[0016] The zinc dithiophosphate represented by the general formula (I) includes compound
of which all the substituents of R¹ - R⁴ in the formula are the same to compound of
which all the substituents of R¹ - R⁴ in the formula are different, and they may be
used singly or used in combination of more than two kinds upon mixing thereof. Normally,
two kinds or more than two kinds of the zinc dithiophosphate whose substituents of
R¹ - R⁴ are same are used upon mixing thereof. However, the compound can be used singly,
and also, two kinds or more than two kinds of the zinc dithiophosphates having the
different four substituents of R¹ - R⁴ may be used singly or in combination with the
zinc dithiophosphates having the same four substituents of R¹ - R⁴. However, in either
cases, it is necessary that the zinc dithiophosphate in which R¹ - R⁴ denote a primary
alkyl group of 3 - 30 carbon atoms is more than 30 weight % based on the whole zinc
dithiophosphate to be used. As the foregoing zinc dithiophosphate, the compounds sold
in the market may be used, for example, Lubrizol 677 (compound in which R¹ - R⁴ are
mostly secondary hexyl group), Lubrizol 1060 (compound in which R¹ - R⁴ are mostly
secondary alkyl group of less than 5 carbon atoms) , Lubrizol 1360 (compound in which
R¹ - R⁴ are mostly mixture of an isobutyl group and n-amyl group), Lubrizol 1370 (compound
in which R¹ - R⁴ are mostly alkylaryl group), Lubrizol 1395 (compound in which R¹
- R⁴ are mostly a primary butyl group and amyl group) sold by Nippon Lubrizol Co.),
or Oloa 260 (compound in which R¹ - R⁴ are mostly an alkylaryl group), Oloa 267 (compound
in which R¹ - R⁴ are mostly a primary hexyl group) sold by Chevron Chemical Corp.,
USA, and furthermore, Santolube 393 (compound in which R¹ - R⁴ are mostly a secondary
hexyl group) sold by Monsant Chemical Co., USA, Amoco 198 (compound in which R¹ -
R⁴ are mostly a primary butyl group and amyl group) sold by Amoco Chemical Co., USA
are used singly or properly in combination by adjustment so that the zinc dithiophosphate
in which R¹ - R⁴ are a primary alkyl radical of 3 - 30 carbon atoms is more than 30
weight % based on the whole zinc dithiophosphate.
[0017] Also, in this invention, the oxymolybdenum organo-phosphorodithioate sulfide represented
by the general formula (II) is used as the (B) component together with or instead
of the zinc dithiophosphate represented by the general formula (I). This oxymolybdenum
organophosphorodithioate is manufactured by the method described in, for example,
Japanese Patent Publication No. 44-27366, and as the concrete compounds, olymolybdenum
di-isopropy phosphorodithioate sulfide, oxymolybdenum di-isobutyl phosphorodithioate
sulfide, oxymolybdenum di(2-ethylhexyl)phosphorodithioate sulfide, oxymolybdenum di-(p-tertiary
butylphenyl)phosphorodithioate sulfide, and oxymolybdenum di-(nonylphenyl)phosphorodithioate
sulfide can be enumerated.
[0018] Zinc dithiophosphate represented by the general formula (I) and/or the oxymolybdenum
organophosphorodithioate sulfide represented by the general formula (II) which is
the (B) component of this invention is the compound having function as an extreme
pressure additive (improve of load carrying capacity, wear resistance), and its blending
rate is in the range of 0.1 - 2.0 weight % to the whole composition, and preferably
0.2 - 1.5 weight %. In case the blending rate is less than 0.1 weight %, the sufficient
addition effect does not appear, and on the other hand, it is not possible to expect
a remarkable effect even if the blending of more than 2.0 weight % is made, and inversely,
showing a tendency of decreased effect.
[0019] Also, in this invention, as the (C) component, 0.1 to 3.0 weight % to the whole composition
of alkenyl succinimide or its derivatives is used. As alkenyl succinimide, a variety
of compounds are available, and for example, many compounds including OLOA-1200N,
OLOA-373 made by Kalonite Chemical Co., LUBRIZOL 6406 made by Nippon Lubrizol, and
HITEC E-638 made by Nippon Couper Co. can be enumerated.
[0020] Furthermore, as the derivative of the alkenyl succinimide, particularly, boron compound
derivative is preferable. As the boron compound derivative of the alkenyl succinimide,
for example, reaction product of alkenyl succinimide and boron compound (for example
boric acid, borate, boric ester), a product prepared by reacting alkyl substituted
succinic acid anhydride with a reaction product of alkylene amine and boron compound
(described in Japanese Patent Publication No. 42-8013), a product prepared by reacting
an alkylene amine with a reaction product of hydrocarbon substituted succinic acid
anhydride and boron compound (described in Japanese Patent Publication No. 42-8014),
prepared by reacting hydroxylated primary amine and boron compound with alkenyl succinic
acid anhydride (described in Japanese Patent Laid-open Publication No. 51-52381),
a product prepared by reacting boron compound with a reaction product obtained by
reacting aromatic polyvalent carboxylic acid, alkenyl succinic acid and polyalkylene
polyamine at a specific molar ratio (described in Japanese Patent Laid-open Publication
No. 51-130408), a condensation product of amino-alcohol and boric acid and oxyethane
carboxylic acid (described in Japanese Patent Laid-open Publication No. 54-87705),
and a product obtained by sequentially reacting polyalkylene glycol, secondary alkanol
amine and boron compound with polyalkenyl succinic acid anhydride, are known. As the
(C) component, the boron compound derivative of the alkenyl succinimide is particularly
preferable.
[0021] The alkenyl succinimide or its derivative, which is the (C) component, does not contain
metal component and shows a function satisfactory for the dispersion of an insoluble
mixture in a lubricant composition, which acts as so called dispersing agent, and
its blending rate is in the range of 0.1 - 3.0 weight % to the whole composition,
preferably, 0.2 - 1.0 weight %. In case, if the blending rate is less than 0.1 weight
%, the addition effect is not sufficient, and also, in case it exceeds 3.0 weight
%, there is not much chance for the rising of the effect.
[0022] Furthermore, in this invention as the (D) component, 0.01 to 1.0 weight to the whole
composition of a rust inhibitor which is calcium sulfonate or barium sulfonate, is
used.
[0023] The rust inhibitor that is the (D) component is blended at a rate of 0.01 - 1.0 weight
% to the whole composition, preferably 0.1 - 0.5 weight %. In case the blending rate
is less than 0.01 weight %, the rust cannot be prevented, and also, in case the blending
rate is more than 1.0 weight %, an improvement of the rust preventing effect cannot
be anticipated, and inversely, showing a tendency of deteriorating the wear resistance
which is not preferable.
[0024] The lubricant composition of this invention is composed of the foregoing (A), (B),
(C) and (D) components, but furthermore, if necessary, proper amount of a variety
of additives may be added. For example phenol antioxidants such as 2,6-ditertiary
butyl-p-cresol, and 4,4'-methylenebis-(2,6-ditertiary butylphenol) can be enumerated.
Also, as the pour point depressant or viscosity index improver, polymethacrylate can
be enumerated, and particularly, the polymethacrylate having number-average molecular
weight 10,000 - 100,000 are preferable. In addition, olefin copolymers such as ethylene-propylene
copolymer and styrene-propylene copolymer can be used. These phenol antioxidants or
pour point depressants or viscosity index improving agents are normally added by 0.1
- 10.0 weight % to the whole composition.
[0025] Furthermore, it is possible to use tricresyl phosphate, triphenyl phosphate, and
trixylenyl phosphate. These compounds may be normally added to the (B) component,
and particularly, in case of using the tricresyl phosphate, 0.1 - 1.5 weight % to
the whole composition, preferably 0.2 - 1.0 weight % may be added.
[0026] Besides, proper amount of corrosion inhibitor, oiliness agent, extreme pressure additive,
defoaming agents, fatigue life improving agent and the like may be added.
[0027] The lubricant composition of this invention consisting of the foregoing component
has particularly high traction coefficient, and high power transmitting efficiency.
[0028] Moreover, the lubricant composition of this invention is excellent in the wear resistance,
load carrying capacity.
[0029] Furthermore, the lubricant composition of this invention is superior in the thermal
stability, oxidation stability, and rust preventing property, and there are no problems
such as generation of sludge or corrosion.
[0030] Accordingly, the lubricant composition of this invention can be extremely effectively
used in the traction drive mechanism including the gear mechanism, oil pressure mechanism,
or rolling contact bearing in the same system, in other words, in the lubrication
of the power transmission having the traction drive mechanism.
[0031] This invention will be described in the following by referring to examples.
Examples 1 - 6 and Comparative Examples 1 - 3:
1) Example of Preparation
[0032] 1000 g of tetralin (tetrahydronaphthalene) and 300 g of concentrated sulfuric acid
were placed into a flask made of glass of 3-litre capacity, and the inside temperature
of the flask was cooled to 0°C in ice bath. And then, 400 g of styrene was dropped
into the solution for 3 hours while stirring thereof and the reaction was completed
in one hour while stirring thereof. Thereafter, the stirring was suspended, and was
allowed to stand to separate the oily layer, and this oily layer was washed with 500
cm³ of 1N-aqueous solution of sodium hydroxide and 500 cm³ of saturated solution of
sodium chloride three times each, and then, it was dried by sodium sulfate anhydride.
Successively, unreacted tetralin was distilled off, and then, distillation under reduced
pressure was carried out to yield 750 g of fraction having boiling point of 135 -
148°C/22.67 Pa (0.17 mmHg). As a result of analysis of this fraction, it was confirmed
to be a mixture of 1-(1-tetralyl)-1-phenylethane and 1-(2-tetralyl)-1-phenylethane.
[0033] Next, 500 cm³ of the fraction was placed into an autoclave of 1-litre capacity, and
50 g of activated nickel catalyst for hydrogenation (trade name N-113 Catalyst made
by Nikki Chemical Co.) was added, and hydrogenation processing was carried out for
4 hours in the reaction condition of hydrogen pressure of 20 kg/cm², and reaction
temperature of 150°C. After the cooling, the reaction solution was filtered and the
catalyst was separated. Successively, light material was stripped from the filtrate,
and an analysis of the resulting product showed that a rate of hydrogenation was more
than 99.9 %, and also this product was confirmed to be a mixture of 1-(1-decalyl)-1-cyclohexylethane
and 1-(2-decalyl)-1-cyclohexylethane. A specific gravity of the resulting mixture
was 0.94 (15/4°C), and dynamic viscosity was 4.4 mm²s⁻¹ (cSt)(100°C), and also, refracting
index n

was 1.5032.
2) Preparation of Lubricant Composition
[0034] The lubricant composition was prepared by adding the component shown in Table 1 to
the base oil ((A) component) at a predetermined rate, and a variety of tests were
carried out on the resulting lubricant composition. The results are shown in Table
1. The method of testing is as follows.
Method of testing
(1) lubricant oxidation stability test for internal combustion engine (ISOT)
[0035] The test was carried out in accordance with 3.1 of JIS K 2514 (150°C x 96 hours).
(2) traction coefficient
[0036] The test was carried out by 2-cylinder type rolling friction testing machine. Namely,
the cylinder A having a curvature (diameter 52 mm, radius of curvature 10 mm) and
the cylinder B having flat surface (diameter 52 mm) were made to contact by 68.6 N
(7000 gf), and the cylinder A was arranged to run at a fixed speed (1500 rpm) and
the cylinder B was arranged to raise the speed from 1500 rpm and the traction force
generated between both the cylinders at the slip rate 5 % was measured to find the
traction coefficient.
[0037] The quality of material of the two cylinders was bearing steel SUJ-2, and the surface
was finished with buff by alumina (0.03 micrometer), and the surface roughness was
less than R
max 0.1 micrometer), and Hertz's contact pressure was 1.098·10⁹ Pa (112 kgf/mm²). The
sample oil was kept at 100°C by temperature control to make measurement.
(3) wear resistance
[0038] The shell four-ball test of ASTM D-4172 was carried out. (Provided that the condition
was 1800 rpm x 30 kg x 2 h·RT).
(4) load resistant performance
[0039] The test was carried out in accordance with ASTM D-2783.
(5) rust preventing property
[0040] The test was carried out in accordance with JIS K 2246.
Comparative Example 4: